Quaternary ammonium compounds



Patented May 4, 1943 UNITED STATES PATENT OFFICE QUATERNARY AMMONIUMCOMPOUNDS Friedrich. Leuchs, Wuppertal-Elberfeld, Germany, assignor toWinthrop Chemical Company, Inc., New .York, N. Y., a corporation oi NewYork No Drawing Application May 28, 1940, Serial No. 337,579. In GermanyMay 11, 1939 9 Claims.

Lower alkyl acid radical R Lower alkyl (cHz) 14.0 0.N

CH: R

in which X stands for the integer 1 or 2 at least one R stands for ahigher molecular aliphatic hydrocarbon radical, the other R. standingfor hydrogen and the aromatic nucleus is substituted by at least onesubstituent of the group consisting of alkyl, alkoxy, halogen and nitro.aliphatic hydrocarbon radicals of 8-18 carbon atoms come intoconsideration as higher molecular aliphatic radicals. The highermolecular aliphatic hydrocarbon radical may contain substituents such asthe hydroxy group, alkoxy and amino groups and halogen atoms or the saidradicals may be interrupted by other atoms such as etherlike boundoxygen and sulfur atoms or in the form of amino groups by nitrogenatoms. It may be mentioned that when using the term higher molecularaliphatic radical in the specification and the appended. claims it isintended to include also the said substitution products or the radicalswhich are interrupted by etherlike bound oxygen or sulfur atoms or inthe form of amino groups by nitrogen atoms. The alkyl groupssubstituting the quaternary nitrogen are preferably lower alkyl groupssuch as methyl, ethyl, propyl, isopropyl, butyl group etc. Asregards thebactericidal action the compounds are especially active which containone of the above mentioned substituents in p-position of the arcmaticnucleus.

The ammonium compounds thus obtainable are in part crystalline, in partthickly liquid substances which in general dissolve in water. They arepractically odorless and relatively non-toxic for men and have provedsuitable for the most various preserving and disinfecting purposes. For

instance, they may be employed for the disinfection of all kinds oftable utensils, storage utensils. They are further advantageously usedfor disinfecting medical instruments, all articles Preferablydisinfected by means of the new quaternary ammonium compounds. Alsofoodstufls such as fruits, vegetables, meat etc. may be preserved ordisinfected.

The new compounds may also be used in dilution with hard water withoutdiminution of their activity. In the concentration necessary fordisinfection they do not injure the skin and therefore may also be usedfor the disinfection of the skin, particularly the hands. As they do notirritate on mucous membranes which are especiall sensitive, they may beadded to gargles, toothpastes and so on for imparting them antisepticproperties.

' The new quaternary compounds may be used in substance as well as insolution or emulsion or in admixture with each other and/or with otheractive or inert substances.

The new quaternary ammonium compounds specified above may be preparedaccording to the methods known per se, for instance, by reacting upon ahalogenacyl amide having linked to the nitrogen atom of the amide groupa higher molecular aliphatic hydrocarbon radical or a hydroaromatichydrocarbon radical with a tertiary amine containing a benzyl radicalwhich is substituted by at least one substituent of the group consistingof alkyl, alkoxy, halogen and nitro. Another way for preparing the newquaternary ammonium compounds consists in treating aminoacyl amides. theamino group of which is in the tertiary state and which contain, linkedto the nitrogen atom a higher molecular aliphatic hydrocarbon radical ora hydroaromatic hydrocarbon radical with alkylating or aralkylatlngagents. When the nitrogen atom of the amino group is not substituted bya benzyl radical carrying at least one of the groups alkyl, alkoxy,halogen and nitro a reactive ester of the benzyl alcohol must be chosenfor this reaction substituted by one of the groups alkyl, alkoxy,halogen and nitro.

Furthermore. it may be started from carboxylic acids or reactivederivatives thereof such as esters or halides carrying a quaternaryammonium group which is substituted by a benzyl radical to which islinked at least one substituent of the groups alkyl, alkoxy, halogen andnitro. Carborwllc acids or their reactive derivatives of this kind maybe transformed according to the usual methods with the aid of highermolecular aliphatic hydrocarbon radicals or hy'droaromatic hydrocarbonradicals containing amines into the corresponding acid amide compounds.

A further way for manufacturing the new com. pounds is as follows: It isstarted from ammonium acyl amide compounds as'specified above but thearomatic nucleus of which being unsubstituted. A substituent of thegroups alkyl, alkoxy, halogen and nitro is then introduced into the 250parts of a 39% alcoholic dimethyl amine solution are added to 261.5parts or chloroacetyldodecylamide (obtainable by reacting dodecylaminewith chloroacetyl chloride in the presence of pyridine or dimethylamine,melting point 61- 63 (3.). The mixture is heated to 90-100 C. in aclosed vessel. When distilled at 2 mm. pressure thedimethylaminoacetyl-dodecyi-amide, boiling point 170-172 C./2 mm. andmelting point 39-41" C. is obtained from the reaction mixture.

171.5 parts of p-nitrobenzyl chloride are added at water bathtemperature on 270 parts 01 the aforesaid product. Thep-nitrobenzyl-dimethylammonium chloride-N-acetyl-dodecylamide isobtained which, recrystallized from acetone-or acetic ester, melts at132-134 C. It is easily soluble in water.

The same product may be obtained in the following manner:

180 parts or p-nitrobenzyldimethylamine are allowed to react with, 261.5parts 01 chloroacetyldodecylamide at water bath temperature withstirring. The p-nitrobenzyl-dimethyl-ammonium chloride-N-acetyldodecylamide is obtained in a crystalline form.

The product kills colibacteria in the concentration of 1: 30000 andstaphylococci in the concentration of 1: 40000 within 2.5 minutes.

Example 2 391 parts of p-nitrobenzyl-methylaminoacetyl dodecylamide(obtainable from p-nitrobenzylmethylamine and chloroacetyl-dodecylamideand purified by means 01 the hydrochloric acid salt, melting point 223,C. from alcohol) are heated to 50 C. with 50.5 parts of chloromethyl ina closed vessel. The p-nitrobenzyl-dimethyl-ammonium chloride-N-acetyldodecyl-amide, obtainable according to this way, is identical with theproduct described in Example 1. Ii. instead of chlormethyl bromomethylor methyl iodide are used, the corresponding bromide or iodide withsimilar properties may be obtained.

Example 3 270 parts .01 dimethylamino-acetyl-dodecylamide are heatedwith 140.5 parts or p-methylbenzyl chloride to 90 C. With evolution 01heat the p-methylbenzyl-dimethyl-ammonium chloride-N-acetyl dodecylamideis obtained. It melts, when recrystallized irom acetic ester, at 153-155 C.

The product kills colibacteria in the concentration or 1: 20000 andstaphylococci in the concentration of 1: 80000 within 2.5 minutes.

Example 4 270 parts of dimethylamino-acetyl-dodecylamide are reactedwith 161 parts 01 p-chlorobenzyl chloride. Alter heating to 80-85 C.with stirring, the temperature rises to -110 C. As reaction product thep-chlorobenzyl-dimethylammonium chloride N acetyl dodecylamide (meltingpoint C. from acetone) is obtained.

The product kills colibacteria in the concentration of 1: 15000 andstaphylococci in the concentrationot 1: 45000 within 2.5 minutes.

In a corresponding manner the p-methoxybenzyl dimethyl-ammonium chlorideN acetyl dodecylamide (melting point 137-139 C.) is obtained byreplacing the p-chlorobenzyl-chloride by 156.5 parts 01' p-methoxybenzylchloride.

The product kills colibacteria in the concentration of 1: 20000 andstaphylococci in the concentration of 1: 30000 within 2.5 minutes.

11 instead of the dodecyl amide of the dimethylamino-acetyl the amidesare used formed with other higher molecular aliphatic or hydroaromaticamines such as, for instance, decylamide, tetradecylamide,hexadecylamide or mixtures thereof, products of similar properties areobtained. Likewise one or more methyl groups may be replaced by otheralkyl radicals.

Example 5 275.5 parts of chloroacetyl-methyl-dodecylamide (obtainablefrom chloroacetyl' chloride and technical methyl-dodecylamine in thepresence of pyridine, boiling point 190-200 C. at 3 mm. pressure) arereacted with 169.5 parts of o- .chlorobenzyl-dimethylamine at water bathtemperature. A semisolid mass is obtained, easily soluble in water andrepresenting essentially the o-chlorobenzyl-dimethyl-ammoniumchloride-N- acetyl-methyl-dodecylamide.

Example 6 261.5 parts of chloroacetyl-dodecylamide are mixed with 204parts of m,p-dichlorobenzyl-dimethylamine and heated until the reactionstarts. The m,p dichlorobenzyldimethyl-ammoniumchloride-N-acetyl-dodecylamide, melting point 151-152C., is-obtained.

The product kills colibacteria in the concentration of 1: 15000 andstaphylococci in the concentration of 1: 40000 within 2.5 minutes.

Example 7.

275.5 parts of p-chloropropionyl-dodecylamide (obtainable fromp-chloropropionic acid chloride and dodecylamine in the presence oi.pyridine. melting point 78-80 C. from methyl alcohol) are added on partsof p-nitrobenzyl-dimethylamine by heating for some time. The reactionproduct is dissolved in water, the undissolved parts are removed byfiltration, it necessary by adding Norit, and the filtrate isevaporated. The p-nitrobenzyl-dimethyl-ammonium chloride N-propionyl-dodecylamide thus obtained melts at 188-189 C. i

I claim:

1. Water-soluble quaternary ammonium salts or the following generalformula R Lower alkyl (CH)x.OO.N

Lower alkyl l ooid radical whereinxstandsiortheint eger1or2atleast one Rstands fora higher molecular aliphatic hydrocarbon radical, the other Rstanding for hydrogen and the aromatic nucleus of the benzyl group beingsubstituted by at least one substituent of the group consisting ofalkyl, alkoxy, halogen and nitro.

2. Water-soluble quaternary ammonium salts of the following generalformula Lower alkyl Hz. C O .N

B Lower alkyl l acid radical wherein at least one R stands for a highermolecular aliphatic hydrocarbon radical, the other R standing forhydrogen and the aromatic nucleus of the benzyl group being substitutedby at least one substituent of the group consisting of alkyl, alkoxy,halogen and nitro.

3. Quaternary ammonium compounds of the following general formula RLower alkyl CH:.C 0 .N

in Lower alkyl l halogcn B Lower alkyl CHM 0.N

Lower alkyl l balogen wherein at least one R stands for a highermolecular aliphatic hydrocarbon radical, the other R standing forhydrogen and the aromatic nucleus of the benzyl group being substitutedby at least one substituent of the group consisting of alkyl, alkoxy,halogen and ultra in p-position.

5. Quaternary ammonium compounds of th following general formula OK; ihalogen H:

wherein R stands for a higher molecular aliphatic hydrocarbon radicaland the aromatic nucleus of the benzyl group being substituted by atleast one substituent of the group consisting of alkyl, alkoxy, halogenand ultra in p-position.

6. The quaternary ammonium compound of the following formula 7. Thequaternary ammonium compound of the following formula 8. The quaternaryammonium compound of the following formula 9. Quaternary ammoniumcompounds of the following general formula:

, B Lower elkyl (OHt)x.CO.N

B Lower alkyl L halogen H.

wherein x stands for an integer from 1 to 2, at least one B. stands fora higher molecular aliphatic hydrocarbon radical, the other R standingfor hydrogen and the aromatic nu lens of the benzyl group beingsubstituted by t least one substituent of the group consisting alkoxy,halcgenand nltro.

FRIEDRICH LE'UCHS.

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